EP4151613B1 - Verfahren zur herstellung von hydriertem bisphenol a - Google Patents

Verfahren zur herstellung von hydriertem bisphenol a

Info

Publication number
EP4151613B1
EP4151613B1 EP22191214.0A EP22191214A EP4151613B1 EP 4151613 B1 EP4151613 B1 EP 4151613B1 EP 22191214 A EP22191214 A EP 22191214A EP 4151613 B1 EP4151613 B1 EP 4151613B1
Authority
EP
European Patent Office
Prior art keywords
hydrogenated bisphenol
bar
minutes
trans
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP22191214.0A
Other languages
English (en)
French (fr)
Other versions
EP4151613A1 (de
Inventor
Kee Yoon Roh
Jung Hee Jang
Je Young Park
Nam Hyun Cho
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kumho Petrochemical Co Ltd
Original Assignee
Korea Kumho Petrochemical Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Korea Kumho Petrochemical Co Ltd filed Critical Korea Kumho Petrochemical Co Ltd
Publication of EP4151613A1 publication Critical patent/EP4151613A1/de
Application granted granted Critical
Publication of EP4151613B1 publication Critical patent/EP4151613B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • C07C29/19—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings
    • C07C29/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds in six-membered aromatic rings in a non-condensed rings substituted with hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a method for preparing hydrogenated bisphenol A comprising the features of the preamble portion of claim 1.
  • Hydrogenated bisphenol A i.e., 2,2-bis(4-hydroxycyclohexyl)propane
  • a polyester resin prepared by polycondensing hydrogenated bisphenol A with a dibasic acid such as phthalic acid or maleic acid exhibits excellent heat resistance and moisture resistance.
  • An epoxy resin prepared by reacting hydrogenated bisphenol A with epichlorohydrin has excellent electrical properties, exhibits less yellowing for not including an aromatic ring, and thus may be used in places requiring weather resistance, and has excellent operability at low viscosity.
  • due to the controversy over the harmfulness of bisphenol A international demand for environment-friendly products as a substitute for bisphenol A is on the increase.
  • hydrogenated bisphenol A prepared by hydrogenation of bisphenol A is a mixture of three types of stereoisomers, i.e., cis/cis isomer, cis/trans isomer, and trans/trans isomer, depending on the three-dimensional structure of the two cyclohexanes bridged by an isopropylidene group.
  • the trans/trans isomer is known to have the most stable structure.
  • a method for preparing hydrogenated bisphenol A comprising the features of the preamble portion of claim 1 is known from US 2018/346398 A1 .
  • US 2018/346398 A1 teaches a hydrogenation method for preparing HBPA having a higher trans/trans isomers ratio from BPA, the hydrogenation method comprises the following steps:
  • the present invention aims at solving the problems of the prior art described above. It is an object of the present invention to provide a method for preparing hydrogenated bisphenol A with a high yield and a high trans/trans isomer ratio.
  • hydrogenated bisphenol A with a high ratio of trans/trans isomer may be prepared in a high yield.
  • the method has a short reaction time and allows the catalyst to be reused, and thus may be applied to an economic and environment-friendly process.
  • bisphenol A refers to 2,2-bis(4-hydroxyphenyl)propane.
  • HBPA hydrogenated bisphenol A
  • the method for preparing hydrogenated bisphenol A comprises: (a) heating a reactor in which bisphenol A, a solvent, and a ruthenium supported catalyst are added; (b) supplying hydrogen into the reactor to react; and (c) blocking the supply of hydrogen to react.
  • Step (a) is a step for adding bisphenol A, a solvent, and a ruthenium supported catalyst, which are the raw materials, to the reactor, and raising the temperature inside by heating the reactor to prepare for the reaction.
  • the solvent any kind of solvent capable of dissolving bisphenol A may be used.
  • the solvent may be an alcohol-type solvent selected from the group consisting of methanol, ethanol, propanol, isopropanol, and combinations of two or more thereof, but is not limited thereto.
  • the ruthenium supported catalyst When the ruthenium supported catalyst is applied to the preparation method, it may be reused in the process for preparing hydrogenated bisphenol A for 20 or more times without an additional input of the catalyst and delay of reaction time. Even when the catalyst is reused, the hydrogenated bisphenol A prepared by the method for preparing hydrogenated bisphenol A according to an embodiment of the present specification may maintain a high yield and a high ratio of trans/trans isomer of the hydrogenated bisphenol A in the product. Due to the high reusability of the catalyst, economic feasibility of the process may be improved, and an environment-friendly process may be designed.
  • the catalyst may be one in which ruthenium is supported in a carrier such as diatomaceous earth, pumice, activated carbon, silica gel, alumina, zirconium oxide, or titanium oxide.
  • the catalyst may be a Ru/C catalyst in which ruthenium is supported in a carbon-based support, but is not limited thereto.
  • the content of ruthenium in the catalyst may be 0.1 to 20% by weight based on the total weight of the catalyst.
  • the content of ruthenium may be 0.1% by weight, 1% by weight, 2% by weight, 3% by weight, 4% by weight, 5% by weight, 6% by weight, 7% by weight, 8% by weight, 9% by weight, 10% by weight, 11% by weight, 12% by weight, 13% by weight, 14% by weight, 15% by weight, 16% by weight, 17% by weight, 18% by weight, 19% by weight, 20% by weight, or a range between any two of these values.
  • the content of the catalyst may be 0.5 to 10 parts by weight based on 100 parts by weight of the bisphenol A.
  • the content of the catalyst may be 0.5 parts by weight, 1 part by weight, 2 parts by weight, 3 parts by weight, 4 parts by weight, 5 parts by weight, 6 parts by weight, 7 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight or a value between any two of these values, but is not limited thereto.
  • the reaction time may increase, thereby degrading the process efficiency, and lowering the ratio of trans/trans isomer of hydrogenated bisphenol A in the final product.
  • Step (b) is a step for performing hydrogenation reaction, i.e., hydrogen addition reaction, and in step (b), hydrogen is supplied to the reactor to react so that hydrogen is added to the aromatic ring of bisphenol A which is the raw material.
  • hydrogenation reaction i.e., hydrogen addition reaction
  • the hydrogen may be supplied at a pressure of 30 to 60 bar.
  • the pressure may be 30 bar, 32 bar, 34 bar, 36 bar, 38 bar, 40 bar, 42 bar, 44 bar, 46 bar, 48 bar, 50 bar, 52 bar, 54 bar, 56 bar, 58 bar, 60 bar or a range between any two of these values.
  • the hydrogen supply pressure deviates from the above range, the yield of hydrogenated bisphenol A may deteriorate.
  • Step (b) may comprise: (b1) supplying hydrogen at a pressure of 30 to 45 bar in a reactor with an internal temperature of 90 to 120°C; and (b2) supplying hydrogen at a pressure of 45 to 60 bar in a reactor with an internal temperature of 120 to 160°C.
  • the yield of hydrogenated bisphenol A may be improved by adjusting the hydrogen supply pressure according to the temperature change inside the reactor.
  • the reaction time in step (b) may be 30 to 180 minutes.
  • the reaction time may be 30 minutes, 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes or a range between any two of these values.
  • the reaction time is shorter than the above range, the hydrogenation reaction may not proceed sufficiently, and thus the yield of hydrogenated bisphenol A may rapidly deteriorate.
  • the reaction time is longer than the above range, process efficiency and economic feasibility may deteriorate.
  • Step (c) is a step for obtaining a product by performing an additional reaction after blocking the hydrogen supply in step (b). By blocking the hydrogen supply and performing an additional reaction, the ratio of trans/trans isomer of the hydrogenated bisphenol A in the product may be improved.
  • the reaction temperature in each of steps (b) and (c) may be 130 to 160°C.
  • the reaction temperature may be 130°C, 135°C, 140°C, 145°C, 150°C, 155°C, 160°C, or a range between any two of these values.
  • the reaction temperature is lower than the above range, the yield of hydrogenated bisphenol A and the ratio of trans/trans isomer of the hydrogenated bisphenol A in the product may deteriorate.
  • the reaction temperature is higher than the above range, the yield of hydrogenated bisphenol A may decrease and the production of impurities may increase.
  • reaction temperature in step (b) and the reaction temperature in step (c) may be the same or different.
  • the reaction pressure in each of steps (b) and (c) may be 30 to 60 bar.
  • the reaction pressure may be 30 bar, 32 bar, 34 bar, 36 bar, 38 bar, 40 bar, 42 bar, 44 bar, 46 bar, 48 bar, 50 bar, 52 bar, 54 bar, 56 bar, 58 bar, 60 bar or a range between any two of these values.
  • the reaction pressure in step (b) and the reaction pressure in step (c) may be the same or different.
  • the reaction time in step (c) may be 40 to 90 minutes.
  • the reaction time may be 40 minutes, 50 minutes, 60 minutes, 70 minutes, 80 minutes, 90 minutes, or a range between any two of these values.
  • the reaction time in step (c) is shorter than the above range, the yield of hydrogenated bisphenol A and the ratio of trans/trans isomer of the hydrogenated bisphenol A in the product may deteriorate.
  • the reaction time is longer than the above range, process efficiency and economic feasibility may deteriorate.
  • the total reaction time in steps (b) and (c) may be 90 to 240 minutes.
  • the total reaction time may be 90 minutes, 100 minutes, 110 minutes, 120 minutes, 130 minutes, 140 minutes, 150 minutes, 160 minutes, 170 minutes, 180 minutes, 190 minutes, 200 minutes, 210 minutes, 220 minutes, 230 minutes, 240 minutes or a range between any two of these values.
  • the method for preparing hydrogenated bisphenol A according to an embodiment of the present specification has a shorter reaction time than the prior art, and thus may improve process efficiency.
  • the method for preparing hydrogenated bisphenol A may improve the yield of hydrogenated bisphenol A and the ratio of trans/trans isomer of hydrogenated bisphenol A in the product by performing an additional reaction after blocking hydrogen supply, and may improve process efficiency and economic feasibility by reducing reaction time as compared to prior art.
  • the ratio of hydrogenated bisphenol A in the product of step (c) may be 96% or more.
  • the ratio may be 96% or more, 96.5% or more, 97% or more, 97.5% or more, 98% or more, 98.5% or more, 99% or more, or 99.5% or more.
  • the hydrogenated bisphenol A in the product of step (c) may be a mixture of cis/cis isomer, cis/trans isomer, and trans/trans isomer, and the content of trans/trans isomer may be the highest among the three types of isomers.
  • the ratio of trans/trans isomer of hydrogenated bisphenol A in the product of step (c) may be 45% or more.
  • the ratio may be 45% or more, 46% or more, 47% or more, 48% or more, 49% or more, 50% or more, 51% or more, 52% or more, 53% or more, 54% or more, or 55% or more.
  • the hydrogenated bisphenol A prepared according to the method for preparing hydrogenated bisphenol A according to an embodiment of the present specification has a high ratio of trans/trans isomer, and thus when applied to a polymer resin polymerization process, performance such as hardness and glass transition temperature of the polymer resin may be improved.
  • the ratio of hydrogenated bisphenol A intermediate in the product of step (c) may be 1.0% or less.
  • the ratio may be 1.0% or less, 0.9% or less, 0.8% or less, 0.7% or less, 0.6% or less, 0.5% or less, 0.4% or less, 0.3% or less, 0.2% or less, or 0.1% or less.
  • the method for preparing hydrogenated bisphenol A may further comprise: (d) purifying the product of step (c) to obtain hydrogenated bisphenol A.
  • Step (d) may be performed through a distillation process after lowering the temperature of the reactor in which the reaction is completed.
  • the purity of hydrogenated bisphenol A after the purification in step (d) may be 97% or more.
  • the purity may be 97% or more, 97.5% or more, 98% or more, 98.5% or more, 99% or more, or 99.5% or more.
  • the product was sampled at 10-minute intervals using a sampling port of the hydrogenation reactor to perform gas chromatography (GC) analysis.
  • GC gas chromatography
  • the reaction was terminated, and the internal temperature of the reactor was lowered to 100°C. Then, the by-product was separated through a distillation process to obtain hydrogenated bisphenol A.
  • the yield of hydrogenated bisphenol A and the content of trans/trans isomer of the hydrogenated bisphenol A increased as the additional reaction time under hydrogen blocking increased.
  • the content of the trans/trans isomer compared to the yield of hydrogenated bisphenol A sharply increased as the reaction time increased.
  • the yield of hydrogenated bisphenol A was the highest, 97.08%, and at time same time, the content of trans/trans isomer of the hydrogenated bisphenol A was also the highest, 54.88%.
  • Example 1 the gas chromatography analysis results of the products obtained after an additional reaction for 70 minutes are summarized in Table 2 below.
  • Table 2 Reaction temperature (°C) Impurity (%) HBPA yield (%) HBPA isomer (%) others (%) cis/cis cis/trans trans/trans
  • Example 1 150 2.33 97.08 5.74 36.46 54.88 0.59
  • Example 2 140 2.12 97.42 5.85 37.59 53.98 0.46
  • Example 3 130 2.24 96.89 7.9 40.77 48.22 0.87
  • the content of trans/trans isomer of the hydrogenated bisphenol A increased as the reaction temperature increased. Accordingly, the ratio of trans/trans isomer of the hydrogenated bisphenol A in the product of Example 1, which was reacted at 150°C, was the highest, 54.88%.
  • the 20-time average yield of hydrogenated bisphenol A was 96.61%, and the 20-time average content of trans/trans isomer of hydrogenated bisphenol A was 52.5%. That is, both the yield of hydrogenated bisphenol A and the content of trans/trans isomer of hydrogenated bisphenol A were kept constant. This confirms that the catalyst has excellent reusability and there was no delay in the reaction time.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Claims (5)

  1. Verfahren zur Herstellung von hydriertem Bisphenol A, umfassend:
    (a) Erhitzen eines Reaktors, in den Bisphenol A, ein Lösungsmittel und ein Ruthenium-Trägerkatalysator zugegeben werden;
    (b) Umsetzen unter Zufuhr von Wasserstoff in den Reaktor;
    (c) Reagieren nach Unterbrechen der Wasserstoffzufuhr;
    dadurch gekennzeichnet, dass
    die Reaktionstemperatur in jedem der Schritte (b) und (c) 130 bis 160 °C beträgt,
    die Reaktionszeit in Schritt (b) 30 bis 180 Minuten beträgt,
    die Reaktionszeit in Schritt (c) 40 bis 90 Minuten beträgt und
    das Verhältnis von trans/trans-Isomeren des hydrierten Bisphenols A im Produkt aus Schritt (c) 45 % oder mehr beträgt.
  2. Verfahren nach Anspruch 1, wobei in Schritt (b) der Wasserstoff bei einem Druck von 30 bis 60 bar zugeführt wird.
  3. Verfahren nach Anspruch 1 oder 2, wobei Schritt (b) umfasst:
    (b1) Zuführen von Wasserstoff bei einem Druck von 30 bis 45 bar in den Reaktor mit einer Innentemperatur von 90 bis 120 °C; und dann
    (b2) Zuführen von Wasserstoff bei einem Druck von 45 bis 60 bar in den Reaktor mit einer Innentemperatur von 120 bis 160 °C.
  4. Verfahren nach einem der Ansprüche 1 bis 3, wobei der Reaktionsdruck in jedem der Schritte (b) und (c) 30 bis 60 bar beträgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der Anteil an hydriertem Bisphenol A im Produkt aus Schritt (c) 96 % oder mehr beträgt.
EP22191214.0A 2021-09-15 2022-08-19 Verfahren zur herstellung von hydriertem bisphenol a Active EP4151613B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020210122926A KR102720628B1 (ko) 2021-09-15 2021-09-15 수소화 비스페놀 에이의 제조방법

Publications (2)

Publication Number Publication Date
EP4151613A1 EP4151613A1 (de) 2023-03-22
EP4151613B1 true EP4151613B1 (de) 2025-08-06

Family

ID=83004818

Family Applications (1)

Application Number Title Priority Date Filing Date
EP22191214.0A Active EP4151613B1 (de) 2021-09-15 2022-08-19 Verfahren zur herstellung von hydriertem bisphenol a

Country Status (8)

Country Link
US (1) US11834395B2 (de)
EP (1) EP4151613B1 (de)
JP (1) JP7405924B2 (de)
KR (1) KR102720628B1 (de)
CN (1) CN115806470A (de)
PL (1) PL4151613T3 (de)
TW (1) TWI852020B (de)
WO (1) WO2023042993A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN119280852B (zh) * 2023-07-10 2026-04-07 中国石油化工股份有限公司 一种精制氢化双酚a的装置、方法及应用
EP4549419A1 (de) 2023-10-31 2025-05-07 Basf Se Herstellung von cycloaliphatischen oder heterocycloaliphatischen verbindungen durch hydrierung aromatischer oder heteroaromatischer verbindungen unter verwendung von wasserstoff mit niedrigem deuteriumgehalt

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1217317B (it) * 1987-05-05 1990-03-22 Montedison Spa Procedimento per l'idrogenazione di bisfenoli
JP2684431B2 (ja) * 1989-11-16 1997-12-03 出光石油化学株式会社 ４，４’―イソプロピリデンジシクロヘキサノールの精製法
JPH069461A (ja) * 1992-06-24 1994-01-18 Nippon Steel Chem Co Ltd 水素化ビスフェノ−ル類の製造方法
JP4182305B2 (ja) * 1998-07-28 2008-11-19 新日本理化株式会社 水素化ビスフェノールａ異性体組成物
JP2003002853A (ja) * 2001-06-21 2003-01-08 Maruzen Petrochem Co Ltd 水素化ビスフェノールａ異性体混合物およびその製造方法
JP2006524744A (ja) 2003-04-25 2006-11-02 ダウ グローバル テクノロジーズ インコーポレイティド 植物油系ポリオール及びそれから製造したポリウレタン
CN102211979A (zh) * 2010-04-02 2011-10-12 盘锦和运新材料有限公司 一种制备2,2-二(4-羟基环己基)丙烷的方法
CN105849074A (zh) * 2013-11-06 2016-08-10 株式会社大赛璐 氢化酚化合物的制造方法、以及氢化酚化合物的分离方法
TWI630954B (zh) * 2014-12-09 2018-08-01 財團法人工業技術研究院 雙酚a或其衍生物的氫化方法以及對苯二甲酸或其衍生物的氫化方法
CN106083529B (zh) * 2016-06-03 2018-09-25 江苏清泉化学股份有限公司 一种氢化双酚a的制备方法及双酚a加氢用催化剂
CN106631826B (zh) * 2016-11-29 2018-04-20 万华化学集团股份有限公司 一种二氨基二环己基甲烷的制备方法
CN106866365B (zh) * 2017-03-30 2020-06-30 威海新元科盛新材料有限公司 一种氢化双酚ａ的连续制备方法
TWI640498B (zh) * 2017-05-31 2018-11-11 南亞塑膠工業股份有限公司 一種產製高反／反異構物比例之氫化型丙二酚的氫化方法
CN109678661B (zh) 2018-12-17 2022-01-25 常州大学 用于连续化制备氢化双酚a的设备及氢化双酚a的连续化制备方法
CN113045384B (zh) * 2020-11-24 2023-01-13 上海徽迪皓新材料科技有限公司 一种氢化双酚a的连续化制备方法
CN113117743B (zh) * 2021-04-06 2022-07-12 万华化学集团股份有限公司 一种加氢催化剂的制备方法及制备氢化双酚a的方法

Also Published As

Publication number Publication date
CN115806470A (zh) 2023-03-17
JP7405924B2 (ja) 2023-12-26
US20230084194A1 (en) 2023-03-16
US11834395B2 (en) 2023-12-05
TW202313537A (zh) 2023-04-01
KR20230039949A (ko) 2023-03-22
KR102720628B1 (ko) 2024-10-23
EP4151613A1 (de) 2023-03-22
JP2023043169A (ja) 2023-03-28
PL4151613T3 (pl) 2025-12-22
WO2023042993A1 (ko) 2023-03-23
TWI852020B (zh) 2024-08-11

Similar Documents

Publication Publication Date Title
US20180346398A1 (en) Hydrogenation method for preparing hydrogenated bisphenol-a having a higher trans/trans isomer ratio
US11834395B2 (en) Method for preparing hydrogenated bisphenol A
US4394523A (en) Catalytic hydrogenation of di (4-aminophenyl) methane
KR20150062911A (ko) 1,4-사이클로헥산디메탄올의 제조 방법
EP2268713B1 (de) Verfahren zur herstellung von polyaminopolyphenyl-methanen mithilfe eines gemischten feststoff-säure-katalysatorsystems
KR102670911B1 (ko) 1,4-사이클로헥산디메탄올의 제조 방법
US10906865B2 (en) Method for producing 1,4-dicyanocyclohexane, 1,4-bis(aminomethyl)cyclohexane and 1,4-cyclohexanedicarboxylic acid
EP1445272B1 (de) Hydrierung von Methylenedianilin-Homologen und damit gehärtete Epoxyharze
KR101639487B1 (ko) 공정 단순화를 위한 트랜스-1,4-사이클로헥산디메탄올 제조장치
RU2803118C1 (ru) Способ получения гидрированного бисфенола a
EP4524122A1 (de) Verfahren zur reinigung einer 1,4-cyclohexandimethanol-zusammensetzung
CN114929658A (zh) 1,4-环己烷二甲醇的制备方法
CN116178120A (zh) 一种乙酰正丙醇的制备方法
KR20230039392A (ko) Odpa 함량이 낮은 3-하이드록시프로피오닉산 용액 및 그 제조 방법
KR101208050B1 (ko) 1,4-시클로헥산 디카르복실산의 제조 방법
TWI602859B (zh) 製備環己烷乙二醇酯及其衍生物的方法
CN116730848B (zh) 一种1,3-双[(三羟甲基)甲基氨基]丙烷的制备方法
CN116217349B (zh) 一种mibk联产异丙醚的方法
CN113149920B (zh) 三嗪类防老剂中间体的制备方法
EP4063346B1 (de) Verfahren zur herstellung von acrylnitril-dimer
CN116917259A (zh) 1,4-环己烷二甲醇组合物及其纯化方法
JPH0749386B2 (ja) ３，３，５−トリメチルシクロヘキサノンの製造方法
KR20080017596A (ko) 하단투입-상단제거 흐름 공정을 이용한 이소프로판올의제조방법
KR20100004631A (ko) 고수율 1,5-디메틸테트랄린의 제조방법
JPH075503B2 (ja) ３，３，５−トリメチルシクロヘキサノンの製造方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN PUBLISHED

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20230831

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C07C 35/21 20060101ALI20250212BHEP

Ipc: C07C 29/19 20060101AFI20250212BHEP

INTG Intention to grant announced

Effective date: 20250305

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602022018807

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20250912

Year of fee payment: 4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20250929

Year of fee payment: 4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20250930

Year of fee payment: 4

Ref country code: AT

Payment date: 20251020

Year of fee payment: 4

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: UPC_APP_0012279_4151613/2025

Effective date: 20251105

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251206

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251106

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251107

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CZ

Payment date: 20250915

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20251106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1821714

Country of ref document: AT

Kind code of ref document: T

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

REG Reference to a national code

Ref country code: CH

Ref legal event code: H13

Free format text: ST27 STATUS EVENT CODE: U-0-0-H10-H13 (AS PROVIDED BY THE NATIONAL OFFICE)

Effective date: 20260324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250819

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20250831

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20251023

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20250806